WO2013172350A1 - Nouvelle nanodispersion de graphène et son procédé de préparation - Google Patents

Nouvelle nanodispersion de graphène et son procédé de préparation Download PDF

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WO2013172350A1
WO2013172350A1 PCT/JP2013/063438 JP2013063438W WO2013172350A1 WO 2013172350 A1 WO2013172350 A1 WO 2013172350A1 JP 2013063438 W JP2013063438 W JP 2013063438W WO 2013172350 A1 WO2013172350 A1 WO 2013172350A1
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ionic liquid
graphene
mixed
dispersion
compound
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PCT/JP2013/063438
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Japanese (ja)
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相田　卓三
パク・チョン
ラビ・サイスワン
道生 松本
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国立大学法人 東京大学
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Priority to US14/400,877 priority Critical patent/US10030155B2/en
Priority to CN201380024682.3A priority patent/CN104284890B/zh
Priority to EP13791216.8A priority patent/EP2851364A4/fr
Priority to KR1020147029675A priority patent/KR101922893B1/ko
Priority to JP2014515640A priority patent/JP6234922B2/ja
Publication of WO2013172350A1 publication Critical patent/WO2013172350A1/fr

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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/50—Mixing liquids with solids
    • B01F23/55—Mixing liquids with solids the mixture being submitted to electrical, sonic or similar energy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F29/00—Mixers with rotating receptacles
    • B01F29/15—Use of centrifuges for mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F31/00—Mixers with shaking, oscillating, or vibrating mechanisms
    • B01F31/80—Mixing by means of high-frequency vibrations above one kHz, e.g. ultrasonic vibrations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/48—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups having nitrogen atoms of sulfonamide groups further bound to another hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/60—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K3/00—Materials not provided for elsewhere
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/50—Mixing liquids with solids
    • B01F23/56—Mixing liquids with solids by introducing solids in liquids, e.g. dispersing or dissolving
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/917—Electroluminescent

Definitions

  • the present invention relates to a novel ionic liquid capable of dispersing graphene at a high concentration, a graphene nano-dispersion using the ionic liquid, and a method for preparing the dispersion.
  • Graphite a carbon material
  • Graphene has a layered structure, one of which is called graphene.
  • Graphene consists only of hexagonal network-bonded carbon atoms, with a thickness of only one carbon atom, extremely high thermal conductivity, and excellent electrical properties such as electrical conductivity. Expected as a nanosheet.
  • Non-Patent Document 1 The Nobel Prize-winning Geim et al. Stuck graphene on cellophane tape, folded it so that the flake was sandwiched between the adhesive surfaces of the tape, and then peeled off the tape again to peel off the graphene. Obtained (Non-Patent Document 1).
  • Non-patent Document 2 a method of obtaining graphene oxide by oxidizing graphite and then exfoliating it in water.
  • the other method is a method of exfoliating graphite in a solvent or a surfactant solution by ultrasonic treatment or the like (liquid phase exfoliation) to obtain graphene dispersed in the liquid.
  • Non-patent Document 2 Non-patent Document 2
  • the level of dispersibility at the present time is about 2 mg / mL, which is still insufficient for developing a wide range of applications.
  • An object of the present invention is to provide a novel ionic liquid capable of dispersing graphene at a high concentration.
  • Viscosity is defined as resistance to flow, but beyond that, the viscosity of a liquid represents the strength of non-covalent interactions between solvent molecules.
  • the present inventors have found that, in a known graphene dispersion having a surface tension approximate value, the higher the viscosity, the more graphene peeling tends to increase.
  • a novel ionic liquid can be provided that gives an extremely high concentration of graphene dispersion by connecting imidazolium-based ionic liquid portions with a core portion of alkylene oxide.
  • Ionic liquid represented by the following general formula (1) (Where R 1 and R 5 may be the same or different and each independently represents a substituted or unsubstituted C1-C7 linear or branched alkyl group; R 2 is represented by the following formula: Here, R 6 and R 7 may be the same or different, each independently represents a C1-C4 linear or branched alkylene group, m represents an integer of 1-5, R 3 and R 4 may be the same or different and each independently represents a hydrogen atom, a substituted or unsubstituted C1-C4 linear or branched alkyl group, X ⁇ represents a counter ion, n represents 0-30.
  • R 1 and R 5 may be the same or different and each independently represents a substituted or unsubstituted C1-C7 linear or branched alkyl group
  • R 2 is represented by the following formula:
  • R 6 and R 7 may be the same or different, each independently represents a C1-C4 linear or branched al
  • a graphene dispersion liquid having an extremely high concentration as compared with the prior art can be obtained.
  • a graphene dispersion liquid having an extremely high concentration as compared with the prior art can be obtained.
  • high dispersibility is obtained by the ionic liquid of the present invention, graphene can be applied to a wide range of applications, for example, many electronic components such as lithium ion secondary batteries and energy storage appliances.
  • the method for preparing a graphene dispersion of the present invention can obtain a high-concentration graphene dispersion by a one-step exfoliation process of graphite without going through graphene oxide. High value.
  • Raman spectrum of graphene powder obtained from graphene dispersion using graphite powder and ionic liquid of the present invention (compound 1) Graphene layer number distribution of graphite Graphene layer number distribution in graphene dispersion obtained by microwave treatment with Compound 1 Graphene layer number distribution in graphene dispersion obtained by ultrasonic wave treatment with Compound 1 Graphene layer number distribution in graphene dispersion obtained by microwave treatment with Compound 3 Graphene layer number distribution in graphene dispersion obtained by microwave treatment with BMIPF 6 Dynamic viscoelastic properties of dispersions before and after microwave treatment with Compound 1
  • Ionic liquid One form of this invention is related with the novel ionic liquid represented by following formula (1).
  • R 1 and R 5 may be the same or different, and each independently represents a substituted or unsubstituted C1-C7 linear or branched alkyl group.
  • R 1 and R 5 are preferably C1-C6 straight chain alkyl groups, ie methyl, ethyl, n-propyl, n-butyl, n-pentyl or n-hexyl, particularly preferably n -Butyl.
  • R 2 is represented by the following formula (2).
  • R 6 and R 7 may be the same or different, and each independently represents a C1-C4 linear or branched alkylene group.
  • R 6 and R 7 are preferably a C2-C4 linear alkylene group, and more preferably an ethylene group.
  • m is an integer of 1 to 5, and preferably m is 2 or 3.
  • the moiety represented by the formula (2) forms a triethylene glycol nucleus, that is, —CH 2 CH 2 OCH 2 CH 2 OCH 2 CH 2 —.
  • the portion represented by the formula (2) functions as a flexible core of an imidazolium salt skeleton having a surface tension in the vicinity of 40 mJ / m 2. In addition, it is considered that it also has a role as a hydrogen acceptor. When this portion is triethylene glycol, it is considered that these characteristics are optimized.
  • R 3 and R 4 may be the same or different and each independently represents a hydrogen atom, a substituted or unsubstituted C1-C4 linear or branched alkyl group. In the present invention, both R 3 and R 4 are preferably hydrogen.
  • X ⁇ represents a counter ion, and is preferably selected from PF 6 ⁇ , (CF 3 SO 2 ) 2 N ⁇ , BF 4 ⁇ , TSFI ⁇ , Cl ⁇ or Br ⁇ .
  • n represents 0-30.
  • n is an integer of 0 to 2
  • the imidazolium salt portion is a dimer, trimer or tetramer.
  • the synthesis of the ionic liquid of formula (1) uses a continuous synthesis method instead of the sequential synthesis method.
  • the ionic liquid of formula (1) consists of several types of n. It is a mixture of compounds, and n is the average of these.
  • the present invention includes the case where the ionic liquid represented by the formula (1) is such a mixture.
  • an ionic liquid can be synthesized by a continuous synthesis method.
  • Scheme 2 is an example of a method for producing an ionic liquid by a continuous synthesis method, and the compound 4 obtained here is a mixture of several kinds of n, and n is an average value thereof.
  • an acetonitrile solution of compound B (1,1 ′-[1,2-ethanediylbis (oxy-2,1-ethanediyl)] bis (imidazole)
  • triethylene glycol bis p-toluenesulfonate
  • any of the ionic liquids represented by the formula (1) can be used as A.
  • R 2 in the formula (1) is a triethylene glycol or tetraethylene glycol group.
  • the volume ratio of A and B may vary depending on the type of the ionic liquid of A.
  • A may be in the range of greater than 0 and less than 1.0, and B of less than 1.0 and greater than 0.
  • a further aspect of the present invention relates to a graphene dispersion comprising graphene and the ionic liquid or mixed ionic liquid of the present invention.
  • graphene is dispersed at a high concentration.
  • graphene has a layer number distribution and is often a mixture of a single layer of graphene and a plurality of layers of graphene.
  • graphene includes not only single-layer graphene but also one in which a plurality of graphene layers, preferably 9 layers or less, are stacked.
  • the graphene dispersion of the present invention preferably contains 10 mg or more, more preferably 20 mg or more, and further preferably 40 mg or more of graphene per 1 ml of the dispersion. Such a dispersion containing graphene at a high concentration can be provided for the first time in the present invention.
  • the graphene dispersion of the present invention is prepared, for example, by the following method, but is not limited thereto.
  • the method for preparing a graphene dispersion in the present invention includes an ionic liquid represented by the formula (1) or a mixed ionic liquid of the ionic liquid and butylmethylimidazolium hexafluorophosphate or butylmethylimidazolium bis (trifluoromethanesulfonyl) imide.
  • the graphite particles that can be used in the preparation method of the present invention have an average particle size of 100 ⁇ m or less, preferably 1 ⁇ m or more and 100 ⁇ m or less.
  • the average particle diameter is the particle size d 50 at an accumulation of 50%.
  • any ultrasonic disperser can be used, but a horn type ultrasonic disperser is preferably used.
  • the frequency of the ultrasonic wave is about 10 kHz to 1 MHz.
  • the amplitude of the ultrasonic wave is about 1 ⁇ m or more and 100 ⁇ m or less (zero-to-peak value).
  • the application time of the ultrasonic wave is not particularly limited, but is usually 1 minute or longer, preferably 1 minute or longer and 6 hours or shorter.
  • any microwave oven can be used.
  • a general microwave oven of 500 W, 2.4 GHz can be used.
  • the microwave application time is not particularly limited, but is usually 10 seconds or longer, preferably 10 seconds to 10 minutes.
  • a low-energy microwave can be applied to 1 to 100 W, 2.4 GHz, for example. In this case, the application time is about 0.2 to 48 hours.
  • the method for preparing a graphene dispersion of the present invention may include a step of centrifuging the liquid after application of ultrasonic waves, and may further include a step of recovering the liquid layer from the mixed solution after centrifugation.
  • the graphene dispersion is obtained by, for example, centrifuging the whole or part of the obtained mixture with a centrifuge and collecting the supernatant. Centrifugation conditions can be appropriately adjusted depending on the desired graphene concentration.
  • the ionic liquid layer was dried over Na 2 SO 4 , concentrated on a rotary evaporator and dried in a vacuum oven with P 2 O 5 at 105 ° C. overnight to give a yellow liquid (44.5 g, 0. 048 mol, yield: 92%).
  • FIG. 1 shows the Raman spectrum of the graphite powder and the graphene powder obtained from the dispersion.
  • A is the spectrum of graphite powder and B is the spectrum of graphene powder.
  • the change in the shape of the two-dimensional peak is due to disordered and unstacked graphene.
  • Example 1 The same experiment as in Example 1 was performed using butylmethylimidazolium hexafluorophosphate as a dispersion medium. The obtained dispersion liquid was confirmed to contain graphene at a concentration of 5.33 mg / ml.
  • Example 2 Compound 1 and butylmethylimidazolium hexafluorophosphate (BMIPF 6 ) were mixed at 0: 100, 35:65, 56:44, 70:30, 100: 0 (volume ratio) to prepare a mixed ionic liquid. Using this mixed ionic liquid as a dispersion medium, the same experiment as in Example 1 was performed. Table 1 shows the measurement results of the graphene concentration of the obtained dispersion.
  • BIPF 6 butylmethylimidazolium hexafluorophosphate
  • Example 3 Compound 3 and BMIPF 6 were mixed at 0: 100, 35:65, 56:44, 70:30, 100: 0 (volume ratio) to prepare a mixed ionic liquid. Using this mixed ionic liquid as a dispersion medium, the same experiment as in Example 1 was performed. Table 1 shows the measurement results of the graphene concentration of the obtained dispersion.
  • a high-concentration graphene dispersion can be provided by using the novel ionic liquid of the present invention. It has also been found that a mixed ionic liquid of the novel ionic liquid of the present invention and BMIPF 6 can provide a higher concentration of graphene dispersion than the use of the novel ionic liquid of the present invention alone.
  • FIG. 2 is a graphene layer number distribution of graphite obtained by adding a graphite to acetonitrile and measuring a Raman spectrum without sonication and centrifugation. From FIG. 2, it can be seen that in graphite not subjected to special dispersion treatment, the number of graphene layers larger than 9 accounts for 60% or more. In the following examples, the graphene layer number distribution was examined using the ionic liquid of the present invention.
  • Example 4 A graphite mixed solution was prepared by adding graphite to the ionic liquid of Compound 1 to a concentration of 100 mg / mL. Using a microwave reactor CEM Discovery, a microwave was applied to the mixture for 30 seconds under the conditions of 100 W and 2.4 GHz to obtain a graphene dispersion.
  • FIG. 3 shows the result of examining the graphene layer number distribution of the obtained graphene dispersion.
  • FIG. 4 shows the results of examining the graphene layer number distribution of the graphene dispersion obtained by applying ultrasonic waves to the above mixed solution for 1 hour.
  • FIG. 3 shows that the ratio of the graphene layers of 1 to 2 is 50% or more by the short-time microwave treatment.
  • Example 5 Using the ionic liquid of Compound 3, in the same manner as in Example 4, a microwave was applied to the graphite mixed liquid to obtain a graphene dispersion.
  • FIG. 5 shows the result of examining the graphene layer number distribution of the obtained graphene dispersion.
  • microwave treatment is an effective means for obtaining a graphene dispersion when the ionic liquid of the present invention is used.
  • the dispersibility is obtained by the ionic liquid of the present invention, it becomes easy to form a graphene film, and the graphene is applied to many electronic components such as lithium ion secondary batteries and energy storage appliances. It becomes possible to do.
  • the manufacturing method of this invention can obtain a high concentration graphene dispersion by the one-step exfoliation process of graphite, without going through a graphene oxide, production efficiency is high and industrially high.

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Abstract

Le problème décrit par la présente invention est de fournir un nouveau liquide ionique susceptible de disperser le graphène à une concentration élevée. Pour ce faire, l'invention concerne un liquide ionique représenté par la formule générale (1). (Dans la formule, R1 et R5 peuvent être identiques ou différents et représentent chacun indépendamment un groupe alkyle en C1 à C7, à chaîne linéaire ou ramifiée, substitué ou non ; R2 est représenté par la formule (2), dans laquelle R6 et R7 peuvent être identiques ou différents et représentent chacun indépendamment un groupe alcényle en C1 à C4, à chaîne linéaire ou ramifiée, substitué ou non, et m représente un entier de 1 à 5 ; R3 et R4 peuvent être identiques ou différents et représentent chacun indépendamment un atome d'hydrogène ou un groupe alkyle en C1 à C4, à chaîne linéaire ou ramifiée, substitué ou non ; X- représente un contre-ion ; et n représente un nombre de 0 à 30).
PCT/JP2013/063438 2012-05-14 2013-05-14 Nouvelle nanodispersion de graphène et son procédé de préparation WO2013172350A1 (fr)

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Application Number Priority Date Filing Date Title
US14/400,877 US10030155B2 (en) 2012-05-14 2013-05-14 Graphene nanodispersion and method for preparing same
CN201380024682.3A CN104284890B (zh) 2012-05-14 2013-05-14 新型石墨烯纳米分散液及其制备方法
EP13791216.8A EP2851364A4 (fr) 2012-05-14 2013-05-14 Nouvelle nanodispersion de graphène et son procédé de préparation
KR1020147029675A KR101922893B1 (ko) 2012-05-14 2013-05-14 신규 그래핀 나노분산액 및 그 조제 방법
JP2014515640A JP6234922B2 (ja) 2012-05-14 2013-05-14 新規グラフェンナノ分散液及びその調製方法

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JP2012111019 2012-05-14
JP2012-111019 2012-05-14
JP2013060376 2013-03-22
JP2013-060376 2013-03-22

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WO2014175449A1 (fr) * 2013-04-26 2014-10-30 国立大学法人 東京大学 Nouvelle nanodispersion de graphène et procédé de préparation associé
WO2015159635A1 (fr) * 2014-04-17 2015-10-22 株式会社Adeka Liquide contenant une substance en couches et son procédé de fabrication
CN105084348A (zh) * 2014-05-20 2015-11-25 中国科学院大连化学物理研究所 一种制备水相可分散的导电石墨烯分散浆液或固体的方法
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JP2016030713A (ja) * 2014-07-29 2016-03-07 住友化学株式会社 成膜方法、膜及び分散液
WO2016056582A1 (fr) * 2014-10-10 2016-04-14 株式会社Adeka Liquide contenant une substance multicouche et son procédé de préparation
JP2017502900A (ja) * 2013-12-26 2017-01-26 エルジー・ケム・リミテッド グラフェンの製造方法
JPWO2016148252A1 (ja) * 2015-03-18 2017-12-28 株式会社Adeka 層状物質含有液及びその製造方法
CN107619618A (zh) * 2017-10-30 2018-01-23 成都新柯力化工科技有限公司 一种改善石墨烯在涂料中分散性的方法
WO2018117013A1 (fr) 2016-12-19 2018-06-28 株式会社Adeka Solution contenant une substance en couches, et son procédé de production
WO2020027041A1 (fr) 2018-07-30 2020-02-06 株式会社Adeka Procédé de production d'un matériau composite
WO2020027023A1 (fr) 2018-07-30 2020-02-06 株式会社Adeka Matériau composite
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TWI624101B (zh) * 2016-09-12 2018-05-11 國立成功大學 以醚基爲架橋之雙陽離子及其離子液體電解質與儲電裝置
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EP2851364A4 (fr) 2015-12-30
KR20150020163A (ko) 2015-02-25
CN107417621A (zh) 2017-12-01
JPWO2013172350A1 (ja) 2016-01-12
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CN104284890B (zh) 2017-08-15
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